Chain multiyne compound, preparation method and application thereof

ABSTRACT

The present invention relates to fields of organic chemistry and organometallic chemistry. The present invention discloses a chain multiyne compound, a preparation method thereof and an application in synthesizing a fused-ring metallacyclic compound. A structure of the chain multiyne compound in the present invention is shown as Formula I below. The present invention also provides a preparation method of the chain multiyne compound and an application thereof in a synthesis of a fused-ring metallacyclic compound. The chain multiyne compound disclosed in the present invention has multiple functional groups and the structure of the chain multiyne compound is adjustable. The chain multiyne compound can also be used to synthesize the fused-ring metallacyclic compound efficiently. The preparation method of the chain multiyne compound disclosed in the present invention is simple, which can be used to prepare the chain multiyne compound rapidly and efficiently.

TECHNICAL FIELD

The present disclosure relates to fields of organic chemistry andorganometallic chemistry, and more specifically, to a chain multiynecompound, a preparation method thereof and an application in preparing afused-ring metallacyclic compound.

BACKGROUND

Pincer ligands are tridentate ligands that bind tightly to threeadjacent coplanar sites of a metal center in a meridional fashion, whichcan be divided into different type according to the coordinate atoms,such as NCN-, PCP-type pincer ligands. The concept was first proposed inthe 1970s. The corresponding metal complexes containing pincer ligandsare named as pincer complexes. Pincer complexes are widely used in thefield of coordination chemistry, organic synthesis, homogeneouscatalysis and material chemistry due to their properties of excellentstability, reactivity and stereoselectivity (Angew. Chem. Int. Ed. 2001,40, 3750-3781). In recent years, pincer complexes not only play animportant role in fields of CC coupling reaction, inert chemicalactivation, but also have important applications in the field of solarcells, for example, the terpyridine ruthenium complex (black dye) beingwidely used as optoelectronic materials.

The structure, reactivity, as well as applications studies of pincercomplexes have achieved significant progress since the pincer complexfirst reported in 1976 (J. Chem. Soc. Dalton Trans 1976, 1020-1024). Atpresent, most of the reported pincer complexes contain pincer ligands ofNCN-(Coord. Chem. Rev., 2007, 251, 610-641; Coord. Chem. Rev., 2004,248, 2275-2282), NNN-, PCP type (Chem. Rev., 2003, 103, 1759-1792), PCO-or SCS-type, in which there is at least one hetero coordination atoms.Pincer complexes with carbon exclusively as the bonding atoms (i.e.,CCC-type pincer complexes) are rare. In 2013, Xia et al. reported novelfused-ring metallacyclic compounds, metallapentalynes, which can beregarded as a new kind of CCC-type pincer complexes (Nat. Chem. 2013, 5,698-703). These CCC-type pincer complexes exhibit unique properties,such as aggregation induced emission enhancement, large Stokes shiftsand long lifetime, broad absorption from the ultraviolet-visible to thenear-infrared region and excellent photoacoustic and photothermalproperties, thus posess potential applications in biomedicine and solarenergy utilization

Although CCC-type pincer complexes have a good application prospect, howto synthesize these complexes efficiently remains a big challenge due tolack of appropriate CCC pincer ligand or ligand precursor. Therefore, adevelopment and synthesis of the CCC-type pincer ligand or CCC-typepincer ligand precursor are particularly important.

SUMMARY

In order to solve a problem of direct synthesizing a fused-ringmetallacyclic compound from a pincer ligand, the present inventionproposes a chain multiyne compound, a preparation method thereof and theapplication thereof in synthesizing a fused-ring metallacyclic compound.The chain multiyne compound provided by the invention has multiplefunctional groups. The preparation method of the chain multiyne compoundis simple; a structure of the chain multiyne compound is adjustable, andcan be directly used to synthesize the metallacyclic compound.

Applicants of the present invention have found that the chain multiynecompound can be used to synthesize a fused-ring metallacyclic compounddirectly as CCC-type pincer ligand by quantities of research.Furthermore, the inventors have found that a chain multiyne compound canbe obtained by performing a metal exchange reaction of a terminal alkynewith an organometallic reagent in an aprotic solvent and furthercontacting and reacting the obtained reaction mixture withalkynylaldehyde or alkynylketone. The chain multiyne compound candirectly react with a metal complex to obtain the fused-ringmetallacyclic compound. Thus, the present invention has been completed.

According to the first aspect of the present invention, this inventiondiscloses a chain multiyne compound, wherein the chain multiyne compoundhas a structure of Formula I shown below:

wherein X is any one of —O—, —S—, —CR₄R₅—, —SiR₆R₇— and —NR₈—; the R₄,R₅, R₆, R₇, R₈ are any one of hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀ ester,C₁-C₂₀ acyl, C₃-C₂₀ cycloalkyl, C₁-C₂₀ alkyl halide, nitrile group,nitryl, substituted or unsubstituted aryl and

respectively and independently.

The R₉ is any one of C₁-C₈ alkyl and substituted or unsubstitutedphenyl.

R₁ is any one of nitrile group, substituted or unsubstituted C₂-C₃₀alkynyl, substituted or unsubstituted C₄-C₃₀ multiyne, substituted orunsubstituted C₃-C₃₀ cumulene, and R₁ does not contain a structure unitof —C≡CCH(OH)C≡C—.

R₂ and R₃ are any one of hydrogen, substituted or unsubstituted aryl,substituted or unsubstituted C₁-C₈ alkyl, substituted or unsubstitutedC₁-C₈ alkoxy, substituted or unsubstituted C₁-C₈ alkyithiol, substitutedor unsubstituted C₃-C₈ cycloalkyl and substituted or unsubstituted C₂-C₈alkynyl, respectively and independently. R₂ and R₃ do not contain astructure unit of —C≡CCH(OH)C≡C—.

m and n are integers from 1-6, respectively, and m+n<8.

According to the second aspect of the present invention, this inventiondiscloses a preparation method of the chain multiyne compound,comprising:

step a: performing a metal exchange reaction of a compound of Formula IIwith an organometallic reagent RM₁ and/or RM₂Z in an aprotic solvent,and obtaining a reaction mixture;

step b: contacting and reacting the obtained reaction mixture with acompound of Formula III, obtaining a reaction mixture containing a chainmultiyne compound with a protection group Y of Formula IV;

step c: taking off the protection group Y from the chain multiynecompound with a protection group Y of Formula IV of the obtainedreaction mixture in step b, and obtaining the chain multiyne compound ofFormula I:

Wherein, Y is any one of trimethylsilyl (TMS), triethylsilyl (TES) andtriisopropylsilyl (TIPS).

R of the organometallic reagent RM₁ and/or RM₂Z is any one of C₁-C₈alkyl, phenyl and —NR₁₀R₁₁. The R₁₀ and R₁₁ are any one of hydrogen,C₁-C₈ alkyl and trimethylsilyl, respectively and independently. M₁ islithium, or sodium or potassium. M₂ is magnesium. Z is chlorine, orbromine or iodine.

Or,

step a: performing a metal exchange reaction of a compound of Formula IIwith an organometallic reagent RM₁ and/or RM₂Z in an aprotic solvent,and obtaining a reaction mixture containing;

step b: reacting the obtained reaction mixture with a compound ofFormula V, obtaining a mixture containing the chain multiyne compound ofFormula I.

Wherein R of the organometallic reagent RM₁ and/or RM₂Z is any one ofC₁-C₈ alkyl, phenyl and —NR₁₀R₁₁. The R₁₀ and R₁₁ are any one ofhydrogen, C₁-C₈ alkyl and trimethylsilyl, respectively andindependently. M₁ of the organometallic reagent RM₁ is lithium, orsodium or potassium. M₂ of the RM₂Z is magnesium. Z of the RM₂Z ischlorine, or bromine or iodine.

According to the third aspect of the present invention, this inventiondiscloses an application of the chain multiyne compound in synthesizinga fused-ring metallacyclic compound.

The chain multiyne compound disclosed in the present invention hasmultiple functional groups and the structure of the chain multiynecompound is adjustable and the chain multiyne compound can also be usedto synthesize a fused-ring metallacyclic compound efficiently. Thepreparation method disclosed in the present invention of the chainmultiyne compound is simple, which is able to prepare the chain multiynecompound rapidly and efficiently.

Other characteristics and advantages of the present invention aredescribed in details by following detailed embodiments.

DETAILED DESCRIPTION

Detailed description of the present invention is given below. It shouldbe understood that, the specific embodiments described herein are onlyused to describe and explain the present invention, and are not intendedto limit the present invention.

According to the first aspect of the present invention, this inventiondiscloses a chain multiyne compound, wherein the chain multiyne compoundhas a structure of Formula I shown below:

wherein X is any one of —O—, —S—, —CR₄R₅—, —SiR₆R₇— and —NR₈—; the R₄,R₅, R₆, R₇, R₈ are any one of hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀ estergroup, C₁-C₂₀ acyl, C₃-C₂₀ cycloalkyl, C₁-C₂₀ alkyl halide, nitrilegroup, nitryl, substituted or unsubstituted aryl and

respectively and independently.

The R₉ is any one of C₁-C₈ alkyl and substituted or unsubstitutedphenyl.

The C₁-C₈ alkyl is any one of methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,neopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, neo-hexyl,sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, neo-heptyl, sec-heptyl,tert-heptyl, n-octyl, isooctyl, neo-octyl, sec-octyl, tert-octyl.

When the R9 is substituted phenyl, a substituent group of thesubstituted phenyl can be a halogen or a C₁-C₈ alkyl. The halogen is anyone of F, Cl, Br, and I. The C₁-C₈ alkyl is the same as just mentionedabove.

Wherein, the C₁-C₂₀ alkyl is any one of methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl,neo-hexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, neo-heptyl,sec-heptyl, tert-heptyl, n-octyl, isooctyl, neo-octyl, sec-octyl,tert-octyl, n-dodecyl, n-cetyl, n-octadecyl, n-eicosyl,

The C₁-C₂₀ ester refers to a group which has a total carbon atom numberof 1-20 and an ester

group, and with one hydrogen absent. For example, the C₁-C₂₀ ester canbe any one of

The C₁-C₂₀ acyl is any one of

The C₃-C₂₀ cycloalkyl is any one of cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodedecyl,cyclooctadecyl, cycloeicosyl.

The C₁-C₂₀ alkyl halide is a substituted C₁-C₂₀ alkyl in which at leastone hydrogen atom is substituted by at least any one of F, Cl, Br, andI.

The aryl group is any one of phenyl, naphthyl, anthryl, phenanthryl,pyrenyl, thienyl, furyl, pyridyl, pyrryl.

A substituent group of the substituted aryl is any one of C₁-C₈ alkyl,C₁-C₈ alkoxy, C₁-C₈ alkylthiol, C₁-C₈ acyl, C₁-C₈ acylamino, C₁-C₈ester, C₁-C₈ carboxyl, C₁-C₈ amido, C₃-C₈ cycloalkyl, halogen, nitryl,and nitrile.

Wherein, the C₁-C₈ alkyl is the same as mentioned above.

The C₁-C₈ alkoxy is any one of methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy,neo-pentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, isohexyloxy,neo-hexyloxy, sec-hexyloxy, tert-hexyloxy, n-heptyloxy, isoheptyloxy,neo-heptyloxy sec-heptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy,neo-octyloxy, sec-octyloxy and tert-octyloxy.

The C₁-C₈ alkyithiol is any one of methylthio, ethylthio, n-propylthio,isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio,n-pentylthio, isopentylthio, neo-pentylthio, sec-pentylthio,tert-pentylthio, n-hexylthio, isohexylthio, neo-hexylthio,sec-hexylthio, tert-hexylthio, n-heptylthio, isoheptylthio,neo-heptylthio, sec-heptylthio, tert-heptylthio, n-octylthio,isooctylthio, neo-octylthio, sec-octylthio and tert-octylthio.

The C₁-C₈ acyl is any one of

The C₁-C₈ acylamino is a group with one hydrogen absent, which has atotal carbon atom number of 1-8 and acylamino

For example, the C₁-C₈ acylamino can be any one of

The C₁-C₈ ester is a group with one hydrogen absent, which has a totalcarbon atom number of 1-8 and ester

the C₁-C₈ ester is any one of

The C₁-C₈ carboxyl is a group with one hydrogen absent, which has atotal carbon atom number of 1-8 and carboxyl

For example, the C₁-C₈ carboxyl can be any one of

The C₁-C₈ amido is any one of methylamino, ethylamino, propylamino,butylamino, pentylamino, hexylamino, heptylamino, octylamino,dimethylamino, diethylamino, dipropylamino and dibutylamino.

The C₃-C₈ cycloalkyl is any one of cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl and cyclooctyl.

The halogen is any one of F, Cl, Br and I.

The R₁ is any one of nitrile group, substituted or unsubstituted C₂-C₃₀alkynyl, substituted or unsubstituted C₄-C₃₀ multiyne, substituted orunsubstituted C₃-C₃₀ cumulene, and R₁ does not contain a structure unitof —C≡CCH(OH)C≡C—.

The substituted or unsubstituted C₂-C₃₀ alkynyl is any one of acetenyl,

The C₄-C₃₀ multiyne is any one of

The C₃-C₃₀ cumulene is a residual alkene which contains more than onecouple of adjacent carbon-carbon double bond (cumulative double bond).The C₃-C₃₀ cumulene is any one of

Wherein, a substituent group of the substituted or unsubstituted C₂-C₃₀alkynyl, the substituted or unsubstituted C₄-C₃₀ multiyne, and thesubstituted or unsubstituted C₃-C₃₀ cumulene is any one of substitutedor unsubstituted aryl, C₁-C₈ alkyl, C₁-C₈ alkoxy, C₁-C₈ alkylthiol,C₃-C₈ cycloalkyl and C₁-C₈ halogen alkyl.

The substituted or unsubstituted acyl, C₁-C₈ alkyl, C₁-C₈ alkoxy, C₁-C₈alkylthiol, C₃-C₈ cycloalkyl is the same as mentioned above.

The C₁-C₈ alkyl halide is a substituted C₁-C₈ alkyl of which at leastone hydrogen atom is substituted by at least any one of F, Cl, Br, andI.

It should be noted that the number of carbon atoms in the substitutedC₂-C₃₀ alkynyl groups described herein is 2-30, excluding a number ofcarbon atoms in the substituent group and only including the number ofcarbon atoms in the alkynyl group. Similarly, any numbers of carbonatoms mentioned in the present invention refer to the number of numberof carbon atoms in the group, excluding the number of carbon atoms inthe substituent group.

The R₂ and R₃ are any one of hydrogen, substituted or unsubstitutedaryl, substituted or unsubstituted C₁-C₈ alkyl, substituted orunsubstituted C₁-C₈ alkoxy, substituted or unsubstituted C₁-C₈alkylthiol, substituted or unsubstituted C₃-C₈ cycloalkyl andsubstituted or unsubstituted C₂-C₈ alkynyl, respectively andindependently. R₂ and R₃ do not contain a structure unit of—C≡CCH(OH)C≡C—.

Wherein, a substituted group of the substituted or unsubstituted C₁-C₈alkyl, the substituted or unsubstituted C₁-C₈ alkoxy, the substituted orunsubstituted C₁-C₈ alkylthiol, the substituted or unsubstituted C₃-C₈cycloalkyl and the substituted or unsubstituted C₂-C₈ alkynyl, is arylor substituted aryl. The aryl or the substituted aryl is same asmentioned above.

The substituted or unsubstituted aryl, C₁-C₈ alkyl, C₁-C₈ alkoxy, C₁-C₈alkylthiol, C₃-C₈ cycloalkyl are the same as mentioned above.

The C₂-C₈ alkynyl is any one of ethynyl, propynyl, 1-butynyl,3-methyl-1-butynyl, 1-pentynyl, 3-methyl-1-pentynyl,4-methyl-1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octynyl and phenylethynyl.

m and n are integers from 1-6, respectively, and m+n<8. For example,under a condition of m+n<8, m and n are 1, 2, 3, 4, 5, or 6,independently and respectively. Specifically, m=1 and n=1, 2, 3, 4, 5,or 6; or m=2 and n=1, 2, 3, 4 and 5; or m=3 and n=1, 2, 3 and 4; or m=4and n=1, 2, and 3; or m=5, n=1 or 2; or m=6, n=1.

Preferably, the X is any one of —O—, —S—, —CH₂—, —C(CH₃)₂—, —CHCH₃—,—C(COOMe)₂-, —C(COOEt)₂-, —C(COCH₃)(COOMe)-, —C(Cy)(COOMe)-,—C(CH₂CH₂Br)₂—, —C(CN)₂—, —C(NO₂)₂—, —SiH₂—, —SiMe₂-, —SiPh₂-, —NH—,

Preferably, the R₁ is any one of nitrile, acetenyl,

Preferably, R₂ or R₃ respectively and independently is any one ofhydrogen, methyl, ethyl, n-propyl, isoproyl, methoxy, ethyoxyl,n-propoxy, isopropoxy, methylthio, ethylthio, cyclopropyl, cyclohexyl,

ethynyl, propynyl,

benzyl and phenethyl.

According to the present invention, preferably, the chain multiynecompound is any one of

According to the second aspect of the present invention, this inventiondiscloses a preparation method of the chain multiyne compound. When thesubstituent group of the chain multiyne compound R₃ is hydrogen, thepreparation method 1 is adopted, comprising:

step a: performing a metal exchange reaction of a compound of Formula IIwith an organometallic reagent RM₁ and/or RM₂Z in an aprotic solvent,and obtaining a reaction mixture;

step b: contacting and reacting the obtained reaction mixture with acompound of Formula III, obtaining a reaction mixture containing a chainmultiyne compound with a protection group Y of Formula IV;

step c: taking off the protection group Y from the chain multiynecompound with a protection group Y of Formula IV of the obtainedreaction mixture in step b, and obtaining the chain multiyne compound ofFormula I.

wherein, Y is a protection group to protect alkynyl, Y is any one oftrimethylsilyl (TMS), triethylsilyl (TES) and triisopropylsilyl (TIPS).X, R1, m and n are respectively all the same as mentioned above.

The R of the organometallic reagent RM₁ and/or RM₂Z is any one of C₁-C₈alkyl, phenyl and —NR₁₀R₁₁. The R₁₀ or R₁₁ of —NR₁₀R₁₁ are any one ofhydrogen, C₁-C₈ alkyl and trimethylsilyl respectively and independently.The C₁-C₈ alkyl is the same as mentioned above. M₁ is lithium, or sodiumor potassium. M₂ is magnesium, Z is chlorine, or bromine or iodine.Preferably, the RM1 is at least any one of methyl lithium, ethyllithium, n-butyl lithium, t-butyl lithium, phenyllithium, lithiumdiisopropylamide and lithium bis (trimethylsilyl) amide. Preferably, theRM₂Z is at least any one of methylmagnesium bromide, ethylmagnesiumbromide, methylmagnesium chloride and ethylmagnesium chloride.

According to the present invention, the protection group Y isdeprotected from the obtained chain multiyne compound with a protectiongroup Y of Formula IV by the deprotection agent, wherein thedeprotection agent is at least one of K₂CO₃, Na₂CO₃, Cs₂CO₃, KF,(n-Bu)₄NF (tetrabutylammonium fluoride), (Et)₄NF (tetraethylammoniumfluoride), (Me)₄NF (tetramethylammonium fluoride) and (n-Pr)₄NF(tetrapropylammonium fluoride).

According to the present invention, before the protection group Y istaken off from the obtained chain multiyne compound with a protectiongroup Y of Formula IV by the deprotection agent, quenching and purifyingprocesses are performed on the reaction mixture of step a which containsthe chain multiyne compound with a protection group Y of Formula IV.Wherein, saturated ammonium chloride and/or water is used as a quenchingagent in the quenching process. The purification process comprisesextracting the chain multiyne compound with a protection group Y ofFormula I by an organic solvent, drying, filtrating, concentrating,chromatographic separating the extracted organic phase, and obtainingthe chain multiyne compound of Formula I. Wherein the organic solvent isat least one of diethyl ether, n-hexane, methylbenzene,1,2-dimethoxyethane, 1,4-dioxane, dichloromethane andtrichloromethaneis. The drying process on the organic phase comprisesusing anhydrous magnesium sulfate and/or anhydrous sodium sulfate. Thechromatographic separating process on the organic phase comprises usingsilica gel column chromatography and/or neutral alumina.

According to the present invention, preferably, after the protectiongroup Y is taken off from the obtained chain multiyne compound with aprotection group Y of Formula IV by the deprotection agent, quenchingand purifying processes are performed on the obtained mixture whichcontains the chain multiyne compound with a protection group Y ofFormula I, the quenching and purifying processes are the same asmentioned above.

According to the second aspect of the present invention, when the R₃ ofthe chain multiyne compound of Formula I is any one of substituted orunsubstituted aryl, substituted or unsubstituted C₁-C₈ alkyl,substituted or unsubstituted C₁-C₈ alkoxy, substituted or unsubstitutedC₁-C₈ alkyl sulphanyl, substituted or unsubstituted C₃-C₈ cycloalkyl andsubstituted or unsubstituted C₂-C₈ alkynyl, the preparation method 2 isadopted, comprising:

step a: performing a metal exchange reaction of a compound of Formula IIwith an organometallic reagent RM₁ and/or RM₂Z in an aprotic solvent,and obtaining a reaction mixture containing;

step b: reacting the obtained reaction mixture with a compound ofFormula V, obtaining a mixture containing the chain multiyne compound ofFormula I.

Wherein, the organometallic reagent RM₁ and/or RM₂Z is the same asmentioned above. X, R₁, R₂, m and n are the same as mentioned above,respectively.

According to the second aspect of the present invention, there is nospecial quantity ratio of the compound of the Formula II to the sum ofthe organometallic agent RM₁ and/or RM₂Z. Preferably, the molar ratio ofthe compound of the Formula II to the sum of the organometallic agentRM₁ and/or RM₂Z is 1:(0.5-1), and preferably 1:(0.9-1). When both RM₁and RM₂Z are comprised, there is no special quantity ratio of thecompound of the Formula II to the sum of the organometallic agent RM₁and/or RM₂Z. RM₁ and RM₂Z can be mixed and used with any molar ratio.

According to the second aspect of the present invention, there is nospecial limitation on the aprotic solvent. Preferably, the aproticsolvent is at least one of benzene, methylbenzene, n-haxane, ethylether,1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, petroleum ether andgasoline.

According to the second aspect of the present invention, the metalexchange reaction is performed of the compound of the Formula II and theorganometallic agent RM₁ and/or RM₂Z under protection of an inert gas.The inert gas is any gas that does not react with catalyst, raw materialor product and does not have any negative effect on the reaction. Theinert gas is at least one of nitrogen gas, helium gas, argon gas andneon gas. The condition of contacting the compound of the Formula IIwith the organometallic agent RM₁ and/or RM₂Z in the aprotic solvent,comprises a temperature at −100-30° C., preferably at −78-0° C., withtime of contact for 0.5-10 hours, preferably for 1-3 hours.

According to the second aspect of the present invention, the conditionof contacting the obtained reaction mixture by contacting the compoundof the Formula II with the organometallic agent RM₁ and/or RM₂Z in anaprotic solvent with the compound of the Formula V, comprises atemperature at −100-30° C., preferably at −78-0° C., with time ofcontact for 0.5-10 hours, preferably for 1-5 hours.

According to the third aspect of the present invention, this inventiondiscloses the application of the chain multiyne compound in synthesizinga fused-ring metallacyclic compound.

According to the present invention, the application of the chainmultiyne compound in synthesizing a fused-ring metallacyclic compoundcomprises obtaining the fused-ring metallacyclic compound by reactingthe chain multiyne compound with the metal complex.

According to the present invention, the metal complex is DE_(a)L_(b).

Wherein, the D is any one of Fe, Co, Ni, Ru, Mn, Re, Cr, Mo, W, V, Nb,Ta, Ti, Zr, Hf, Rh, Pd, Ir, Pt and Os.

The E is any one of H, F, Cl, Br, I, SCN and CN.

The L is any one of a phosphine ligand, a CO ligand, a pyridine ligand,a N-heterocyclic carbene ligand, a nitrile ligand and an isocyanoidligand.

Preferably, the L is any one of trimethylphosphine, triethylphosphine,tripropylphosphine, triisopropylphosphine, tritertbutylphosphine,tricyclohexylphosphine, triphenylphosphine, methylpyridine,ethylpyridine, 1, 4-bipyridine, 1,2-bis(4-pyridyl)ethylene,vinylpyridine, pyridine-3-boronic acid, aminopyridine, cyanopyridine,pyridinethiol, ethynylpyridine, dimethylaminopyridine, ethylenepyridine, phenylpyridine, 1,2-bis(4-pyridyl)ethane, imidazoleN-heterocyclic carbene, imidazoline N-heterocyclic carbene, thiazoleN-heterocyclic carbene, triazole N-heterocyclic carbene, acetonitrile,propionitrile, benzonitrile, cyclohexylisocyanide, tert-butylisocyanideand phenylsocyanide.

The a and b are integers from 0-6, respectively; when a≧2, E isdifferent or is the same and when b≧2, L is different or is the same.

Preferably, the metal complex is any one of OsCl₂(PPh₃)₃, RuCl₂(PPh₃)₃,RhCl(PPh₃)₃ and IrHCl₂(PPh₃)₃.

The present invention is hereinafter described in details by specificembodiments.

Embodiment 1

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

Wherein, TMS represents trimethylsilyl, EtMgBr is ethylmagnesium bromide(purchased from J & K Technology Co., Ltd., and a trademark number is248474),

is 3-trimethylsilylpropynal (purchased from J & K Technology Co., Ltd.,and a trademark number is 2975-46-4), (n-Bu)₄NF is tetrabutylammoniumfluoride (purchased from J & K Technology Co., Ltd., and a trademarknumber is A10588).

Step 1. the preparation of the compound 1 (see above)

1,6-heptadiyne (5.0 mL, 4.02 g, 43.63 mmol, purchased from AladdinReagent (Shanghai) Co., Ltd., and a trademark number is H102744-25 mL)was dissolved into 100 mL tetrahydrofuran under an atmosphere of N2 andmagnetic stirring.

The solution was cooled to 0° C., a solution of ethylmagnesium bromide(1.0 M tetrahydrofuran solution, 43.6 mL, and containing ethylmagnesiumbromide 43.60 mmol) was added gradually within 1 h.

The solution reacted for another 1 h at room temperature and then cooledto 0° C.

Trimethylsilylpropynal (7.30 mL, 43.60 mmol) was added rapidly andreacted for 1 h.

After reaction, the solution was quenched with saturated ammoniumchloride, and the solution was extracted with diethyl ether.

The organic phase was merged and the organic phase was dried withanhydrous magnesium sulfate.

The organic solution was filtrated, concentrated to dryness. The residuewas chromatographed with silica gel (eluent:n-hexane:ethylacetate=6:1(v/v)) to obtain 5.71 g compound 1 as colorless oily liquid.A yield is 60%. (The yield of compound 1 is calculated as a molar amountof the compound 1 divided by a molar amount of 1,6-heptanedyne×100%.)

NMR data and high resolution mass spectrometry data of the compound 1are as follows.

¹H NMR δ=5.04 (t, J=1.80 Hz, 1H), 2.69 (br, 1H), 2.31 (td, J=6.99 Hz,J=1.80 Hz, 2H), 2.25 (td, J=6.99 Hz, J=2.60 Hz, 2H), 1.93 (t, J=2.60 Hz,1H), 1.69 (m, 2H), 0.14 (s, 9H); ¹³C NMR δ=102.71, 88.81, 84.24, 83.45,78.31, 69.12, 52.59, 27.25, 17.82, 17.56, −0.26. HRMS-ESI (m/z)calculated value C₁₃H₁₈OSiNa [M+Na]⁺ 241.1019, measured value 241.1025.

Step 2. the preparation of the compound 2 (see above).

The compound 1 (5.0 g, 22.90 mmol) was dissolved into 120 mLtetrahydrofuran.

The solution was cooled to 0° C. A solution of tetrabutylammoniumfluoride (1.0 M tetrahydrofuran solution, 27.48 mL, containingtetrabutylammonium fluoride 27.48 mmol) was slowly added.

The reaction was stopped until the raw materials disappeared (about 30min).

The reaction solution was quenched with saturated ammonium chloride, andthen extracted with diethyl ether.

The organic phase was merged and the organic phase was dried withanhydrous magnesium sulfate.

The organic solution was filtrated, concentrated to dryness. The residuewas chromatographed with silica gel (eluent:n-hexane/ethyl acetate witha volume ratio of 4/1) to obtain 2.85 g compound 2 as colorless oilyliquid. Yield is 85%. (The yield of compound 2 is calculated as a molaramount of the compound 2 divided by a molar amount of the compound1×100%.)

NMR data and high resolution mass spectrometry data of the compound 2are as follows.

¹H NMR δ=5.08 (m, 1H), 2.69 (br, 1H), 2.53 (t, J=2.20 Hz, 1H), 2.34 (td,J=7.00 Hz, J=1.85 Hz, 2H), 2.25 (td, J=7.00 Hz, J=2.57 Hz, 2H), 1.95 (t,J=2.57 Hz, 1H), 1.71 (m, 2H); ¹³C NMR δ=84.65, 83.49, 81.52, 77.91,72.39, 69.22, 52.06, 27.18, 17.77, 17.62. HRMS-ESI (m/z) calculatedvalue C₁₀H₁₀OSiNa [M+Na]⁺ 169.0624, measured value 169.0651.

Embodiment 2

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

Wherein, n-BuLi represents n-butyllithium (purchased from J & KTechnology Co., Ltd., and a trademark number is 913796).

Step 1. the preparation of the compound 3 (see above)

2,2-dimethyl dipropargylmalonate (5.0 g, 24.0 mmol, synthesizedaccording to literature J. Am. Chem. Soc. 2013, 135, 8133.) wasdissolved into 200 mL tetrahydrofuran under an atmosphere of N₂ andmagnetic stirring.

The solution was cooled to −78° C., n-butyllithium (2.2 Mtetrahydrofuran solution, 10.90 mL, containing n-butyllithium 24.0 mmol)was added gradually for 1 h.

The solution reacted at −78° C. for 15 mins.

Trimethylsilylpropynal (3.52 mL, 24.0 mmol) was added rapidly andreacted for 2 h.

After reaction, the solution was quenched with saturated ammoniumchloride, and the solution was extracted with diethyl ether.

The organic phase was merged and the organic phase was dried withanhydrous magnesium sulfate.

The organic solution was filtrated, concentrated to dryness. The residuewas chromatographed with silica gel (eluent:n-hexane:ethyl acetate=5:1(v/v)) to obtain 4.82 g compound 3 as light yellow oily liquid. Theyield is 60%. (The yield of compound 3 is calculated as a molar amountof the compound 3 divided by a molar amount of 2,2-dimethyldipropargylmalonate×100%.)

NMR data and high resolution mass spectrometry data of the compound 3are as follows.

¹H NMR δ=5.03 (s, 1H), 3.76 (s, 6H), 3.03 (d, J=2.00 Hz, 2H), 2.97 (d,J=2.64 Hz, 2H), 2.37 (br, 1H), 2.03 (t, J=2.60 Hz, 1H), 0.19 (s, 9H);¹³C NMR δ=169.05, 102.11, 88.97, 81.08, 79.06, 78.28, 71.88, 56.59,53.14, 52.30, 22.93, 22.77, −0.41; HRMS-ESI (m/z) calculated valueC₁₇H₂₂O₅SiNa [M+Na]⁺357.1129, measured value 357.1130.

Step 2. the preparation of the compound 4 (see above).

The compound 3 (4.82 g, 14.4 mmol) was dissolved into 150 mLtetrahydrofuran.

The solution was cooled to −30° C., a solution of tetrabutylammoniumfluoride (1.0 M tetrahydrofuran solution, 21.6 mL, containingtetrabutylammonium fluoride 21.6 mmol) was added slowly.

The solution reacted until the raw materials disappear (about 20 min).

The reacted solution was quenched with saturated ammonium chloride, andthe solution was extracted with diethyl ether. The organic phase wasdried with anhydrous magnesium sulfate.

The organic solution was filtrated, concentrated to dryness. The residuewas chromatographed with silica gel (eluent:n-hexane:ethylacetate=3:1(v/v)) to obtain 3.21 g compound 4 as light yellow oilyliquid. Yield is 85%. (The yield of compound 4 is calculated as a molaramount of the compound 4 divided by a molar amount of the compound4×100%.)

NMR data and high resolution mass spectrometry data of the compound 4are as follows.

¹H NMR δ=5.05 (ddt, J=7.51 Hz, J=2.25 Hz, J=2.11 Hz, 1H), 3.76 (s, 1H),3.02 (d, J=2.11 Hz, 2H), 2.95 (d, J=2.72 Hz, 2H), 2.81 (d, J=7.51 Hz,1H), 2.53 (d, J=2.25 Hz, 1H), 2.03 (t, J=2.68 Hz, 1H); ¹³C NMR δ=169.11,80.99, 80.78, 79.03, 78.19, 72.44, 72.10, 56.48, 53.25, 51.54, 22.84,22.75; HRMS-ESI (m/z) calculated value C₁₄H₁₄O₅Na [M+Na]⁺ 285.0733,measured value 285.0734.

Embodiment 3

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

Step 1. the preparation method of compound 5 is the same as that ofcompound 1, except the following characteristics:

the 1,6-heptadiyne used in embodiment 1 is replaced by dipropargyl ether(purchased from Alfa Aesar (China) Chemical Co., Ltd., and a trademarknumber is MFCD00048108) with an equal molar amount.

Yield of compound 5 is 75%. The yield of compound 5 is calculated as amolar amount of the compound 5 divided by a molar amount of dipropargylether×100%.

NMR data and high resolution mass spectrometry data of the compound 5are as follows.

¹H NMR δ=5.14 (t, J=1.67 Hz, 1H), 4.31 (d, J=1.67 Hz, 1H), 4.24 (b,J=2.37 Hz, 2H), 2.47 (br, 1H), 2.46 (t, J=2.37 Hz, 1H), 0.17 (s, 9H);¹³C NMR δ=101.60, 89.95, 84.19, 79.74, 78.85, 75.40, 56.81, 56.75,52.59, −0.22; HRMS-ESI (m/z) calculated value C₁₂H₁₆O₂SiNa [M+Na]⁺243.0812, measured value 248.0805.

Step 2. the preparation method of compound 6 is the same as that ofcompound 2, except the following characteristics:

the compound 1 in step 2 of embodiment 1 is replaced by the compound 5in step 1 of the present embodiment.

The yield of the compound 6 is 87%. (The yield of compound 6 iscalculated as a molar amount of the compound 6 divided by a molar amountof the compound 5×100%.)

NMR data and high resolution mass spectrometry data of the compound 6are as follows.

¹H NMR δ=5.16 (s, 1H), 2.69 (br, 1H), 4.31 (d, J=1.52 Hz, 1H), 4.25 (d,J=2.25 Hz, 2H), 2.80 (br, 2H), 2.57 (d, J=2.25 Hz, 1H), 2.47 (t, J=2.25Hz, 1H); ¹³C NMR δ=83.81, 80.69, 80.09, 78.82, 75.47, 73.13, 56.87,56.76, 52.05; HRMS-ESI (m/z) calculated value C₉H₈O₂Na [M+Na]⁺ 171.0417,measured value 171.0411.

Embodiment 4

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

Step 1. the preparation method of compound 7 is the same as that ofcompound 1, except the following characteristics:

the 1,6-heptadiyne used in embodiment 1 is replaced byN,N-Dipropargyl-p-toluenesulfonamide (synthesized according toliterature J. Am. Chem. Soc. 2000, 122, 11529.) with an equal molaramount.

Yield of compound 7 is 60%. The yield of compound 7 is calculated as amolar amount of the compound 7 divided by a molar amount ofN,N-Dipropargyl-p-toluenesulfonamide×100%.

NMR data and high resolution mass spectrometry data of the compound 7are as follows.

¹H NMR δ=7.64 (d, J=12.34 Hz, 2H), 7.35 (d, J=12.34 Hz, 2H), 5.16 (t,J=1.64 Hz, 1H), 3.95 (d, J=1.64 Hz, 2H), 3.87 (d, J=2.37 Hz, 2H), 2.65(br, 1H), 2.49 (t, J=2.37 Hz, 1H), 2.34 (s, 3H), 0.13 (s, 9H); ¹³C NMRδ=137.50, 136.79, 129.87, 128.37, 102.50, 87.85, 84.11, 80.74, 78.64,74.80, 52.64, 34.83, 34.55, 21.56, −0.32; HRMS-ESI (m/z) calculatedvalue C₁₉H₂₃NSO₃SiNa [M+Na]⁺ 396.1060, measured value 396.1058.

Step 2. the preparation method of compound 8 is the same as that ofcompound 2, except the following characteristics.

The compound 1 in step 2 of embodiment 1 is replaced by the compound 7in step 1 of the present embodiment.

The yield of the compound 8 is 81%. The yield of compound 8 iscalculated as a molar amount of the compound 8 divided by a molar amountof the compound 7×100%.

NMR data and high resolution mass spectrometry data of the compound 8are as follows.

¹H NMR δ=7.63 (d, J=12.37 Hz, 2H), 7.32 (d, J=12.37 Hz, 2H), 5.19 (dt,J=2.35 Hz, J=1.64 Hz, 1H), 3.93 (d, J=1.64 Hz, 2H), 3.85 (d, J=2.36 Hz,2H), 2.55 (br, 1H), 2.52 (d, J=2.35 Hz, 1H), 2.47 (t, J=2.36 Hz, 1H),2.33 (s, 3H); ¹³C NMR δ=137.48, 136.72, 129.77, 128.27, 87.835, 84.01,80.33, 78.54, 74.58, 72.76, 52.53, 34.92, 34.48, 21.57; HRMS-ESI (m/z)calculated value C₁₆H₁₅NSO₃Na [M+Na]⁺ 324.0665, measured value 324.0661.

Embodiment 5

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

Step 1. the preparation method of compound 9 is the same as that ofcompound 1, except:

the 1,6-heptadiyne used in embodiment 1 is replaced by 1,7-octadiyne(purchased from Alfa Aesar (China) Chemical Co., Ltd., and a trademarknumber is MFCD0000880) with an equal molar amount.

The yield of compound 9 is 45%. The yield of compound 9 is calculated asa molar amount of the compound 9 divided by a molar amount of1,7-octadiyne×100%.

NMR data and high resolution mass spectrometry data of the compound 9are as follows.

¹H NMR δ=5.07 (t, J=1.97 Hz, 1H), 2.55 (br, 1H), 2.25 (td, J=7.00 Hz,J=1.85 Hz, 2H), 2.20 (td, J=7.00 Hz, J=2.80 Hz, 2H), 1.95 (t, J=2.51 Hz,1H), 1.63 (m, 4H), 0.17 (s, 9H); ¹³C NMR δ=102.62, 88.75, 84.91, 84.06,77.82, 68.67, 52.55, 27.40, 27.13, 18.22, 17.09, −0.33; HRMS-ESI (m/z)calculated value C₁₄H₂₀OSiNa [M+Na]⁺ 255.1176, measured value 255.1152.

Step 2. the preparation method of compound 10 is the same as that ofcompound 2, except the following characteristics:

the compound 1 in step 2 of embodiment 1 is replaced by the compound 9in step 1 of the present embodiment.

The yield of the compound 10 is 78%. The yield of compound 10 iscalculated as a molar amount of the compound 10 divided by a molaramount of the compound 9×100%.

NMR data and high resolution mass spectrometry data of the compound 10are as follows.

¹H NMR δ=5.08 (d, J=2.20 Hz, 1H), 2.90 (br, 1H), 2.54 (d, J=2.25 Hz,1H), 2.23 (td, J=6.57 Hz, J=1.97 Hz, 2H), 2.19 (td, J=6.65 Hz, J=2.54Hz, 2H, 2H), 1.95 (d, J=2.59 Hz, 1H), 1.60 (m, 4H); ¹³C NMR δ=85.21,84.14, 76.83, 72.28, 68.77, 51.91, 27.38, 27.10, 18.15, 17.88; HRMS-ESI(m/z) calculated value C₁₁H₁₂ONa [M+Na]⁺ 183.0780, measured value183.0785.

Embodiment 6

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

Step 1. the preparation method of compound 11 is the same as that ofcompound 3, except the following characteristics:

the 2,2-dimethyl dipropargylmalonate used in embodiment 2 is replaced by5-cyano-1-pentyne (purchased from J & K Technology Co., Ltd., and atrademark number is 009109) with an equal molar amount.

The compound 11 is light yellow oily liquid. The yield of compound 11 is81%. The yield of compound 11 is calculated as a molar amount of thecompound 11 divided by a molar amount of 5-cyano-1-pentyne×100%.

NMR data and high resolution mass spectrometry data of the compound 11are as follows.

¹H NMR δ=5.07 (t, J=1.85 Hz, 1H), 2.54 (br, 1H), 2.48 (t, J=7.08 Hz,2H), 2.41 (td, J=6.74 Hz, J=1.85 Hz, 2H), 1.87 (tt, J=7.08 Hz, J=6.74Hz, 2H), 0.17 (s, 9H); ¹³C NMR δ=119.23, 102.22, 89.39, 82.51, 79.59,52.60, 24.29, 17.99, 16.23, −0.22. HRMS-ESI (m/z) calculated valueC₁₂H₁₇NOSiNa [M+Na]⁺ 242.0972, measured value 242.0968.

Step 2. the preparation method of compound 12 is the same as that ofcompound 4, except the following characteristics:

the compound 3 in step 2 of embodiment 2 is replaced by the compound 11in step 1 of the present embodiment.

The compound 12 is light yellow oily liquid. Yield of the compound 12 is87%. The yield of compound 12 is calculated as a molar amount of thecompound 12 divided by a molar amount of the compound 11×100%.

NMR data and high resolution mass spectrometry data of the compound 12are as follows.

¹H NMR δ=5.09 (dd, J=2.00 Hz, J=1.70 Hz, 1H), 2.65 (br, 1H), 2.56 (d,J=2.00 Hz, 1H), 2.49 (t, J=7.13 Hz, 2H), 2.42 (td, J=6.73 Hz, J=1.70 Hz,2H), 1.88 (tt, J=7.13 Hz, J=6.73 Hz, 1H); ¹³C NMR δ=119.28, 82.79,81.24, 79.25, 72.63, 52.01, 24.21, 17.94, 16.29. HRMS-ESI (m/z)calculated value C₉H₉NONa [M+Na]⁺ 170.0576, measured value 170.0583.

Embodiment 7

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

Step 1. the preparation method of compound 13 is the same as that ofcompound 3, except the following characteristics:

the 2,2-dimethyl dipropargylmalonate used in embodiment 2 is replaced by4-propargyloxy-1,2-butadiene (synthesized according to literature Eur J.Org. Chem. 2013, 15, 3041, and PCT Int. Appl., 2011050016) with an equalmolar amount.

The compound 13 is light yellow oily liquid. The yield of compound 13 is55%. The yield of compound 13 is calculated as a molar amount of thecompound 13 divided by a molar amount of4-propargyloxy-1,2-butadiene×100%.

NMR data and high resolution mass spectrometry data of the compound 13are as follows.

¹H NMR δ=5.20 (tt, J=6.69 Hz, J=6.69 Hz, 1H), 5.15 (t, J=1.84, 1H), 4.78(dt, J=6.69 Hz, J=2.34 Hz, 2H), 4.23 (d, J=1.84 Hz, 2H), 4.12 (dt,J=6.69 Hz, J=2.34 Hz, 2H), 2.68 (br, 1H), 0.11 (s, 9H); ¹³C NMRδ=209.36, 101.23, 86.51, 83.24, 80.67, 80.12, 75.67, 72.53, 67.32,56.91, 52.35; HRMS-ESI (m/z) calculated value C₁₃H₁₈O₂SiNa [M+Na]⁺257.0968, measured value 257.0986.

Step 2. the preparation method of compound 14 is the same as that ofcompound 4, except the following characteristics:

the compound 3 in step 2 of embodiment 2 is replaced by the compound 13in step 1 of the present embodiment.

The compound 14 is light yellow oily liquid. The yield of the compound14 is 87%. The yield of compound 14 is calculated as a molar amount ofthe compound 14 divided by a molar amount of the compound 13×100%.

NMR data and high resolution mass spectrometry data of the compound 14are as follows.

¹H NMR δ=5.22 (tt, J=6.71 Hz, J=6.71 Hz, 1H), 5.16 (dt, J=1.84 Hz,J=1.84, 1H), 4.81 (dt, J=6.71 Hz, J=2.35 Hz, 2H), 4.23 (d, J=1.84 Hz,2H), 4.09 (dt, J=6.71 Hz, J=2.35 Hz, 2H), 2.71 (br, 1H), 2.57 (d, J=1.84Hz, 1H); ¹³C NMR δ=209.57, 86.81, 83.45, 80.77, 80.13, 76.01, 72.81,67.46, 56.81, 51.50; HRMS-ESI (m/z) calculated value C₁₀H₁₀O₂Na [M+Na]⁺185.0573, measured value 185.0574.

Embodiment 8

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

Step 1. the preparation method of compound 15 is the same as that ofcompound 3, except the following characteristics:

the 2,2-dimethyl dipropargylmalonate used in embodiment 2 is replaced by2-propargyl-2-(5-phenyl-2,4-pentadiynyl) dimethyl malonate (synthesizedaccording to literature J. Am. Chem. Soc. 2008, 130, 14713.) with anequal molar amount.

The compound 15 is light yellow oily liquid. Yield of compound 15 is45%. The yield of compound 15 is calculated as a molar amount of thecompound 15 divided by a molar amount of2-propargyl-2-(5-phenyl-2,4-pentadiynyl) dimethyl malonate×100%.

NMR data and high resolution mass spectrometry data of the compound 15are as follows.

¹H NMR δ=7.30-7.48 (m, 5H), 5.04 (dt, J==7.61 Hz, J=2.02 Hz, 1H), 3.79(s, 6H), 3.16 (s, 2H), 3.07 (d, J=2.02 Hz, 2H), 2.35 (d, J=7.61 Hz, 1H),0.19 (s, 9H); ¹³C NMR δ=168.86, 132.57, 129.16, 128.56, 101.99, 89.28,81.30, 79.12, 77.82, 75.92, 68.30, 56.73, 53.29, 52.45, 24.06, 23.29,−0.36; HRMS-ESI (m/z) calculated value C₂₅H₂₆O₅SiNa [M+Na]⁺ 457.1442,measured value 457.1450.

Step 2. the preparation method of compound 16 is the same as that ofcompound 4, except the following characteristics:

the compound 3 in step 2 of embodiment 2 is replaced by the compound 15in step 1 of the present embodiment.

The compound 16 is light yellow solid. Yield of the compound 16 is 89%.The yield of compound 16 is calculated as a molar amount of the compound16 divided by a molar amount of the compound 15×100%.

NMR data and high resolution mass spectrometry data of the compound 16are as follows.

¹H NMR δ=7.29-7.48 (m, 5H), 5.07 (dt, J=2.25, J=2.29, 1H), 3.80 (s, 6H),3.16 (s, 2H), 3.07 (d, J=2.29 Hz, 2H), 2.55 (d, J=2.25 Hz, 1H), 2.19(br, 1H); ¹³C NMR δ=168.89, 132.59, 129.20, 128.40, 121.52, 80.93,79.33, 77.74, 75.99, 73.78, 72.56, 68.37, 56.67, 53.39, 51.86, 24.10,23.25; HRMS-ESI (m/z) calculated value C₂₂H₁₈O₅Na [M+Na]⁺ 385.1046,measured value 385.1049.

Embodiment 9

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

The preparation method of compound 17 is the same as that of compound 1,except the following characteristics:

the 1,6-heptadiyne used in embodiment 1 is replaced by propargyl etherwith an equal molar amount. The 3-trimethylsilylpropynal in embodiment 1is replaced by phenyl propargyl aldehyde

(synthesized according to literature Org. Lett. 2012, 14, 4906.) with anequal molar amount.

Yield of compound 17 is 70%. The yield of compound 17 is calculated as amolar amount of the compound 17 divided by a molar amount of propargylether×100%.

NMR data and high resolution mass spectrometry data of the compound 17are as follows.

¹H NMR δ=7.43-7.45 (m, 2H), 7.29-7.33 (m, 3H), 5.20 (t, J=1.65 Hz, 1H),4.33 (d, J=1.65 Hz, 2H), 4.26 (d, J=2.23 Hz 2H), 2.70 (br, 1H), 2.46 (t,J=2.23 Hz, 1H); ¹³C NMR δ=131.79, 128.72, 128.32, 122.01, 89.93, 88.26,82.62, 78.85, 77.71, 75.42, 52.12, 56.72, 56.61; HRMS-ESI (m/z)calculated value C₁₅H₁₂O₂Na [M+Na]⁺ 247.0730, measured value 247.0726.

Embodiment 10

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

The preparation method of compound 18 is the same as that of compound 1,except the following characteristics:

the 1,6-heptadiyne used in embodiment 1 is replaced by propargyl etherwith an equal molar amount. The 3-trimethylsilylpropynal in embodiment 1is replaced by p-tolylpropynal

(synthesized according to literature Org. Lett. 2012, 14, 4906.) with anequal molar amount.

Yield of compound 18 is 62%. The yield of compound 18 is calculated as amolar amount of the compound 18 divided by a molar amount of propargylether×100%.

NMR data and high resolution mass spectrometry data of the compound 18are as follows.

¹H NMR δ=7.42-7.44 (m, 2H), 7.26-7.30 (m, 2H), 5.21 (t, J=1.66 Hz, 1H),4.30 (d, J=1.66 Hz, 2H), 4.27 (d, J=2.24 Hz 2H), 2.66 (br, 1H), 2.45 (t,J=2.24 Hz, 1H), 2.35 (s, 3H); ¹³C NMR δ=131.74, 128.70, 128.29, 122.11,89.92, 88.29, 82.60, 78.83, 77.73, 75.45, 52.16, 56.73, 56.62, 27.45;HRMS-ESI (m/z) calculated value C₁₆H₁₄O₂Na [M+Na]⁺ 261.0886, measuredvalue 261.0882.

Embodiment 11

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

The preparation method of compound 19 is the same as that of compound 1,except the following characteristics:

the 1,6-heptadiyne used in embodiment 1 is replaced by propargyl etherwith an equal molar amount. The 3-trimethylsilylpropynal in embodiment 1is replaced by 4-phenyl-3-butyn-2-one

(purchased from Alfa Aesar (China) Chemical Co., Ltd., and a trademarknumber is MFCD0000877) with an equal molar amount.

Yield of compound 19 is 65%. The yield of compound 19 is calculated as amolar amount of the compound 19 divided by a molar amount of propargylether×100%.

NMR data and high resolution mass spectrometry data of the compound 19are as follows.

¹H NMR δ=7.44-7.46 (m, 2H), 7.30-7.34 (m, 3H), 4.34 (s, 2H), 4.27 (d,J=2.22 Hz 2H), 2.59 (br, 1H), 2.46 (t, J=2.22 Hz, 1H), 1.87 (s, 3H); ¹³CNMR δ=131.81, 128.74, 128.31, 122.03, 89.94, 88.27, 82.61, 78.87, 77.70,75.40, 60.23, 56.74, 56.62, 31.89; HRMS-ESI (m/z) calculated valueC₁₆H₁₄O₂Na [M+Na]⁺ 261.0886, measured value 261.0879.

Embodiment 12

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

The preparation method of compound 20 is the same as that of compound 1,except the following characteristics:

the 1,6-heptadiyne used in embodiment 1 is replaced by propargyl etherwith an equal molar amount. The 3-trimethylsilylpropynal in embodiment 1is replaced by 3-pentyn-2-one

(synthesized according to J. Am. Chem. Soc. 2008, 130, 14713.) with anequal molar amount.

Yield of compound 20 is 60%. The yield of compound 20 is calculated as amolar amount of the compound 20 divided by a molar amount of propargylether×100%.

NMR data and high resolution mass spectrometry data of the compound 20are as follows.

¹H NMR δ=4.35 (s, 2H), 4.29 (d, J=2.30 Hz 2H), 2.85 (br, 1H), 2.46 (t,J=2.30 Hz, 1H), 1.85 (s, 3H), 1.92 (s, 3H); ¹³C NMR δ=86.64, 85.27,82.01, 78.57, 77.50, 75.20, 59.73, 56.62, 56.50, 31.59, 5.4; HRMS-ESI(m/z) calculated value C₁₁H₁₂O₂Na [M+Na]⁺ 199.0730, measured value199.0727.

Embodiment 13

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

The preparation method of compound 21 is the same as that of compound 1,except the following characteristics:

the 1,6-heptadiyne used in embodiment 1 is replaced by propargyl etherwith an equal molar amount. The 3-trimethylsilylpropynal in embodiment 1is replaced by 1-phenyl-2-butyn-1-one

synthesized according to J. Am. Chem. Soc. 2008, 130, 14713.) with anequal molar amount.

Yield of compound 21 is 60%. The yield of compound 21 is calculated as amolar amount of the compound 21 divided by a molar amount of propargylether×100%.

NMR data and high resolution mass spectrometry data of the compound 21are as follows.

¹H NMR δ=7.35-7.31 (m, 2H), 7.11-7.15 (m, 3H), 4.36 (s, 2H), 4.29 (d,J=2.28 Hz 2H), 2.85 (br, 1H), 2.48 (t, J=2.28 Hz, 1H), 1.93 (s, 3H); ¹³CNMR δ=131.20, 129.34, 127.11, 121.72, 86.82, 85.05, 82.11, 78.93, 77.81,75.52, 65.71, 56.24, 56.12, 8.29; HRMS-ESI (m/z) calculated valueC₁₆H₁₄O₂Na [M+Na]⁺ 261.0886, measured value 261.0878.

Embodiment 14

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

The preparation method of compound 22 is the same as that of compound 1,except the following characteristics:

the 1,6-heptadiyne used in embodiment 1 is replaced by propargyl etherwith an equal molar amount. The 3-trimethylsilylpropynal in embodiment 1is replaced by 4-phenyl-2-butyn-1-al

synthesized according to Angew. Chem., Int. Ed. 2014, 53, 4154.) with anequal molar amount.

Yield of compound 22 is 68%. The yield of compound 22 is calculated as amolar amount of the compound 22 divided by a molar amount of propargylether×100%.

NMR data and high resolution mass spectrometry data of the compound 22are as follows.

¹H NMR δ=7.24-7.26 (m, 2H), 7.13-7.22 (m, 3H), 5.14 (br, 1H), 2.65 (br,1H), 4.30 (d, J=1.57 Hz, 2H), 4.25 (d, J=2.27 Hz, 2H), 2.59 (d, J=2.25Hz, 1H), 3.25 (d, J=1.60 Hz, 2H); ¹³C NMR δ=83.85, 80.75, 80.55, 80.13,78.82, 75.47, 56.85, 56.746, 52.13; HRMS-ESI (m/z) calculated valueC₁₆H₁₄O₂Na [M+Na]⁺ 261.0886, measured value 261.0878.

Embodiment 15

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

The preparation method of compound 23 is the same as that of compound 1,except the following characteristics:

the 1,6-heptadiyne used in embodiment 1 is replaced by propargyl etherwith an equal molar amount. The 3-trimethylsilylpropynal in embodiment 1is replaced by cyclohexyl propylaldehyde

synthesized according to Angew. Chem., Int. Ed. 2014, 53, 4154.) with anequal molar amount.

Yield of compound 23 is 71%. The yield of compound 23 is calculated as amolar amount of the compound 23 divided by a molar amount of propargylether×100%.

NMR data and high resolution mass spectrometry data of the compound 23are as follows.

¹H NMR δ=5.12 (t, J=1.53 Hz, 1H), 2.75 (br, 1H), 4.33 (d, J=1.53 Hz,2H), 4.27 (d, J=2.23 Hz, 2H), 2.57 (d, J=2.23 Hz, 1H), 1.75 (m, 4H),1.56 (m, 6H); ¹³C NMR δ=87.53, 83.85, 80.83, 80.63, 78.87, 75.67, 56.86,56.75, 52.76, 33.52, 28.94, 25.63, 25.19; HRMS-ESI (m/z) calculatedvalue C₁₅H₁₈O₂Na [M+Na]⁺ 253.1199, measured value 253.1198.

Embodiment 16

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

The preparation method of compound 24 is the same as that of compound 1,except the following characteristics:

the 1,6-heptadiyne used in embodiment 1 is replaced by propargyl etherwith an equal molar amount. The 3-trimethylsilylpropynal in embodiment 1is replaced by phenyl pentdialkylaldehyde

(synthesized according to J. Org. Chem. 2013, 78, 12018.) with an equalmolar amount.

Yield of compound 24 is 54%. The yield of compound 24 is calculated as amolar amount of the compound 24 divided by a molar amount of propargylether×100%.

NMR data and high resolution mass spectrometry data of the compound 24are as follows.

¹H NMR δ=7.30-7.48 (m, 5H), 5.17 (t, J=1.69 Hz, 1H), 4.32 (d, J=1.69 Hz,2H), 4.28 (d, J=2.27 Hz, 2H), 2.60 (d, J=2.27 Hz, 1H), 2.53 (br, 1H);¹³C NMR δ=132.48, 129.19, 128.35, 121.32, 81.23, 79.53, 77.64, 75.87,73.54, 73.15, 72.56, 71.76, 56.85, 56.67, 52.86; HRMS-ESI (m/z)calculated value C₁₇H₁₂O₂Na [M+Na]⁺ 271.0730, measured value 271.0726.

Embodiment 17

The present embodiment is to prepare the chain multiyne compounddisclosed in the present invention.

The preparation method of compound 25 is the same as that of compound 3,except the following characteristics:

the 2,2-dimethyl dipropargylmalonate used in step 1 of embodiment 2 isreplaced by dimethyl 2-propargyl-2-(5-phenyl-2,4-pentadiynyl) malonate(synthesized according to literature J. Am. Chem. Soc. 2008, 130,14713.) with an equal molar amount. The 3-trimethylsilylpropynal isreplaced by 3-pentyn-2-one

(synthesized according to literature J. Am. Chem. Soc. 2007, 129, 3826.)with an equal molar amount.

Yield of compound 25 is 50%. The yield of compound 25 is calculated as amolar amount of the compound 25 divided by a molar amount of2,2-dimethyl dipropargylmalonate×100%.

NMR data and high resolution mass spectrometry data of the compound 25are as follows.

¹H NMR δ=7.30-7.48 (m, 5H), 3.77 (s, 6H), 3.15 (s, 2H), 3.09 (s, 2H),2.65 (br, 1H), 1.75 (s, 3H), 1.80 (s, 3H); ¹³C NMR δ=168.87, 132.55,129.16, 128.35, 121.42, 80.90, 79.31, 77.69, 75.87, 73.43, 72.24, 56.66,53.35, 51.92, 31.58, 24.20, 23.31, 10.67; HRMS-ESI (m/z) calculatedvalue C₂₄H₂₂O₅Na [M+Na]⁺ 413.1359, measured value 413.1358.

Embodiment 18

The present embodiment is to describe an application of the chainmultiyne compound disclosed in the present invention in synthesizing thefused-ring metallacyclic compound.

Wherein, DCM is dichloromethane. OsCl₂(PPh₃)₃ (500 mg, 0.48 mmol,synthesized according to literature Inorg. Synth., 1989, 26, 184.) andPPh₃ (629 mg, 2.40 mmol, purchased from Sinopharm Chemical Reagent Co.,Ltd., a trademark number is 80136926) were dissolved into 20 mLdichloromethane under an atmosphere of N2 and magnetic stirring.

A dichloromethane (dissolving 0.72 mmol HC≡CCH(OH)C≡C(CH₂)₃C≡CH into 2mL dichloromethane solution) solution of HC≡CCH(OH)C≡(CH₂)C≡CH (105 mg,0.72 mmol, the synthesis of this compound, refer to embodiment 1) wasadded gradually.

The solution reacted for 1.5 h at room temperature and a color of thesolution was changed from green to red and a reaction mixture wasobtained.

The obtained reaction mixture was concentrated under vacuum to 2 mL.

The concentrated mixture was washed with Et₂O (diethyl ether) for 3times, with 30 mL of diethyl ether at each time.

450 mg of red solid Os-1 was obtained, and yield is 80%. The yield ofOs-1 is calculated as a molar amount of the Os-1 divided by a molaramount of OsCl₂(PPh₃)₃×100%.

NMR data and high resolution mass spectrometry data of the Os-1 are asfollows.

¹H-NMR (300.1 MHz, CD₂Cl₂): δ=13.33 (s, 1H, C⁷H), 7.61 (s, 1H, C³H),7.02-7.79 (m, 45H, Ph), 2.44. (dt, J(HH)=7.27 Hz, J(HH)=3.63 Hz, 2H,C¹⁰H), 2.01 (tt, apparent quint, J(HH)=7.27 Hz, 2H, C⁹H), 1.79 (t,J(HH)=7.27 Hz, 2H, C⁸H); ³¹P{¹H} NMR (121.5 MHz, CD₂Cl₂): δ=5.76 (t,J(PP)=5.72 Hz, CPPh₃), 3.23 (d, J(PP)=5.72 Hz, OsPPh₃); ¹³C{¹H} NMR(75.5 MHz, CD₂Cl₂, plus ¹³C-dept 135, ¹H-¹³C HSQC and ¹H-¹³C HMBC): δ321.56 (dt, apparent q, J(PC)=13.33 Hz, J(PC)=13.33 Hz, C¹), 216.58 (t,J(PC)=10.59 Hz, C⁷), 180.44 (s, C⁵), 175.50 (t, J(PC)=3.53 Hz, C⁶),172.04 (dt, J(PC)=23.30 Hz, J(PC)=3.21 Hz, C⁴), 147.96 (dt, J(PC)=15.36Hz, J(PC)=2.77 Hz, C³), 128.00-135.48 (Ph), 125.89 (dt, J(PC)=95.84 Hz,J(PC)=3.61 Hz, C²), 120.56 (d, J(PC)=90.83 Hz, Ph), 31.32 (s, C⁸), 29.57(s, C¹⁰), 29.28 (s, C⁹). HRMS (ESI): m/z calculated value[C₆₄H₅₃ClP3Os]⁺, 1141.2658; measured value, 1141.2646.

Embodiment 19

The present embodiment is to describe an application of the chainmultiyne compound disclosed in the present invention in synthesizing thefused-ring metallacyclic compound (osmapentalyne Os-2).

A preparation method of Os-2 is the same as that of Os-1 of embodiment18, except the following characteristics:

the HC≡CCH(OH)C≡C(CH₂)₃C≡CH used in embodiment 18 is replaced byHC≡CCH(OH)C≡CCH₂OCH₂C≡CH (the preparation method of this compound refersto embodiment 3) with an equal molar amount.

Red solid Os-2 is obtained, and its yield is 82%. The yield of Os-2 iscalculated as a molar amount of the Os-2 divided by a molar amount ofOsCl₂(PPh₃)₃×100%.

NMR data and high resolution mass spectrometry data of the Os-2 are asfollows.

¹H-NMR (300.1 MHz, CD₂Cl₂): δ=13.27 (s, 1H, C⁷H), 7.69 (s, 1H, C³H),7.01-7.79 (Ph 46H, Ph and above-mentioned C³H), 4.55 (s, C⁹H), 3.89 (s,C⁸H); ³¹P{¹H} NMR (121.5 MHz, CD₂Cl₂): δ=6.05 (t, J(PP)=4.67 Hz, CPPh₃),2.49 (d, J(PP)=4.67 Hz, OsPPh₃); ¹³C{¹H} NMR (75.5 MHz, CD₂Cl₂, plus¹³C-dept 135, ¹H-¹³C HSQC and ¹H-¹³C HMBC): δ 302.51 (dt, apparent q,J(PC)=13.54 Hz, J(PC)=13.54 Hz, C¹), 211.53 (t, J(PC)=11.06 Hz, C⁷),172.79 (s, C⁵), 171.55 (t, J(PC)=4.96 Hz, C⁶), 169.26 (dt, J(PC)=23.95Hz, J(PC)=2.97 Hz, C⁴), 150.34 (d, J(PC)=15.37 Hz, C³), 120.27-135.82(Ph), 119.81 (d, J(PC)=90.43 Hz, C²), 71.39 (s, C⁸), 69.17 (s, C⁹); HRMS(ESI): m/z calculated value [C₆₃H₅₁ClOP₃Os]⁺, 1143.2451; measured value,1143.2435.

Embodiment 20

The present embodiment is to describe an application of the chainmultiyne compound disclosed in the present invention in synthesizing thefused-ring metallacyclic compound (osmapentalyne Os-3).

A preparation method of Os-3 is the same as that of Os-1 of embodiment18, except the following characteristics:

the HC≡CCH(OH)C≡C(CH₂)₃C≡CH used in embodiment 18 is replaced byHC≡CCH(OH)C≡CCH₂C(COOMe)₂CH₂C≡CH (the preparation method of thiscompound refers to embodiment 2) with an equal molar amount.

Red solid Os-3 is obtained, and its yield is 85%. The yield of Os-3 iscalculated as a molar amount of the Os-3 divided by a molar amount ofOsCl₂(PPh₃)₃×100%.

NMR data and high resolution mass spectrometry data of the Os-3 are asfollows.

¹H-NMR (500.2 MHz, CD₂Cl₂): δ=13.16 (s, 1H, C⁷H), 7.67 (s, 1H, C³H),7.02-7.80 (m, 46H, Ph and above-mentioned C³H), 3.64 (s, 6H, COOCH₃),3.12 (s, C¹⁰H), 2.44 (s, C⁸H); ³¹P{¹H} NMR (202.5 MHz, CD₂Cl₂): δ=5.79(t, J(P,P)=5.00 Hz, CPPh₃), 3.31 (d, J(P,P)=5.00 Hz, OsPPh₃); ¹³C{¹H}NMR (125.8 MHz, CD₂Cl₂, plus ¹³C-dept 135, ¹H-¹³C HSQC and ¹H-¹³C HMBC):δ 321.57 (dt, apparent q, J(PC)=13.33 Hz, J(PC)=13.33 Hz, C¹), 217.23(q, J(P,C)=9.78 Hz, J(P,C)=19.55 Hz, C⁷), 173.07 (s, C⁵), 172.16 (s,COOCH₃), 171.81 (d, J(P,C)=23.02 Hz, C⁴), 170.12 (s, C⁶), 149.22 (d,J(P,C)=16.31 Hz, C³), 128.18-135.61 (Ph), 128.15 (dt, J(P,C)=81.30 Hz,J(PC)=3.64 Hz, C²), 120.30 (d, J(PC)=91.07 Hz, Ph), 64.38 (s, C⁹), 53.54(s, COOCH₃), 39.07 (s, C⁸), 37.62 (s, C¹⁰); HRMS (ESI): m/z calculatedvalue [C₆₈H₅₇ClO₄P₃Os]⁺, 1257.2768; measured value, 1257.2771.

Embodiment 21

The present embodiment is to describe an application of the chainmultiyne compound disclosed in the present invention in synthesizing thefused-ring metallacyclic compound (ru-pentalyne Ru-1).

A preparation method of Ru-1 is the same as that of Os-1 of embodiment18, except the following characteristics:

the HC≡CCH(OH)C≡C(CH₂)₃C≡CH used in embodiment 18 is replaced byHC≡CCH(OH)C≡CCH₂C(COOMe)₂CH₂C≡CH (the preparation method of thiscompound refers to embodiment 2) with an equal molar amount.

Red solid Ru-1 is obtained, and its yield is 70%. The yield of Ru-1 iscalculated as a molar amount of the Ru-1 divided by a molar amount ofRuCl₂(PPh₃)₃×100%.

NMR data and high resolution mass spectrometry data of the Ru-1 are asfollows.

¹H NMR (300.1 MHz, CD₂Cl₂): δ=13.06 (s, 1H, C⁷H), 7.33 (1H, C³H,obtained by HSQC), 6.99-7.81 (46H, Ph and above-mentioned C³H), 3.64 (s,6H, COOCH₃), 2.96 (t, J(H,H)=3.63, C¹⁰H), 2.76 (s, C⁸H); ³¹P{¹H} NMR(121.5 MHz, CD₂Cl₂): δ=29.59 (d, J(P,P)=5.89 Hz, RuPPh₃), 6.38 (t,J(P,P)=5.89 Hz, CPPh₃); ¹³C{¹H} NMR (75.5 MHz, CD₂Cl₂, plus ¹³C-dept135, ¹H-¹³C HSQC and ¹H-¹³C HMBC): δ=356.95 (br, C¹), 251.89 (t,J(P,C)=11.96, C⁷), 190.23 (dt, J(P,C)=25.65 Hz, J(P,C)=4.90 Hz, C⁴),180.98 (d, J(P,C)=1.97 Hz, C⁵), 171.77 (s, COOCH₃), 164.57 (t,J(P,C)=4.24 Hz, C⁶), 154.99 (dt, J(P,C)=14.44 Hz, J(P,C)=3.07 Hz, C³),128.18-135.76 (other aromatic carbons), 122.86 (dt, J(P,C)=92.99 Hz,J(P,C)=4.02 Hz, C²), 119.57 (other aromatic carbons), 64.14 (s, C⁹),53.63 (s, COOCH₃, obtained by ¹³C-dept 135), 39.06 (s, C⁸), 37.35 (s,C¹⁰); HRMS (ESI): m/z calculated value [C₆₈H₅₇ClO₄P₃Ru]⁺, 1167.2212;measured value, 1167.2215.

Embodiment 22

The present embodiment is to describe an application of the chainmultiyne compound disclosed in the present invention in synthesizing thefused-ring metallacyclic compound (rhodium double five-membered ringcompound Rh-1).

A preparation method of Ru-2 is the same as that of Os-1 of embodiment18, except the following characteristics:

the HC≡CCH(OH)C≡C(CH₂)₃C≡CH used in embodiment 18 is replaced byHC≡CCH(OH)C≡CCH₂C(COOMe)₂CH₂C≡CH (the preparation method of thiscompound refers to embodiment 2) with an equal molar amount. TheOsCl₂(PPh₃)₃ is simultaneously replaced by RhCl(PPh₃)₃.

Yellow solid Ru-2 is obtained, and its yield is 91%. The yield of Ru-2is calculated as a molar amount of the Ru-2 divided by a molar amount ofRhCl(PPh₃)₃×100%.

NMR data and high resolution mass spectrometry data of the Ru-2 are asfollows.

¹H-NMR (600.1 MHz, CD₂Cl₂): δ=10.27 (d, J(PH)=29.75 Hz, 1H, C¹H),6.87-8.20 (45H, Ph), 6.53 (s, 1H, C⁷H), 3.57 (s, 3H, COOCH₃), 3.54 (s,3H, COOCH₃), 3.45 (d, J(HH)=8.95 Hz, 1H, C³H), 2.35 (d, J(HH)=16.47 Hz,1H, C¹⁰H), 2.27 (d, J(HH)=16.47 Hz, 1H, C¹⁰H), 2.01 (d, J(HH)=17.02 Hz,1H, C⁸H), 1.78 (d, J(HH)=17.02 Hz, 1H, C⁸H), 0.17 (d, J(HH)=8.95 Hz, 1H,OH); ³¹P{¹H} NMR (242.9 MHz, CD₂Cl₂): δ=33.33 (ddd, J(PP)=431.55 Hz,J(RhP)=126.88 Hz, J(PP)=5.74 Hz, RhPPh₃), δ=31.04 (ddd, J(PP)=431.55 Hz,J(RhP)=126.88 Hz, J(PP)=5.74 Hz, RhPPh₃), 8.00 (br, CPPh₃); ¹³C{¹H} NMR(150.5 MHz, CD₂Cl₂, plus ¹³C-dept 135, ¹H-¹³C HSQC and ¹H-¹³C HMBC):δ=221.27 (br, C¹), 174.08 (s, COOCH₃), 173.27 (s, COOCH₃), 167.45 (br,C⁴), 154.85 (s, C⁶), 153.49 (br, C⁷), 145.57 (s, C⁵), 127.32-136.42(Ph), 122.91 (d, J(PC)=46.59 Hz, C²), 122.89 (d, J(PC)=84.89 Hz, Ph),80.32 (d, J(PC)=25.69 Hz, C³), 64.39 (s, C⁹), 52.90 (s, COOCH₃), 52.70(s, COOCH₃), 39.06 (s, C¹⁰), 36.01 (s, C¹⁰); HRMS (ESI): m/z calculatedvalue [C₆₈H₆₀ClO₅P₃Rh]⁺, 1187.2392 [M+H]⁺; measured value, 1187.2418.

Embodiment 23

The present embodiment is to describe an application of the chainmultiyne compound disclosed in the present invention in synthesizing thefused-ring metallacyclic compound (Ir-pentalene Ir-1).

A preparation method of Ir-1 is the same as that of Os-1 of embodiment18, except the following characteristics:

the OsCl₂(PPh₃)₃ used in embodiment 18 is replaced by IrHCl₂(PPh₃)₃ (thepreparation method of this compound refers to embodiment 1).

Yield of Ir-1 is 35%. The yield of Ru-2 is calculated as a molar amountof the Ir-1 divided by a molar amount of IrHCl₂(PPh₃)₃×100%.

NMR data and high resolution mass spectrometry data of the Ir-1 are asfollows.

¹H-NMR (600.1 MHz, CDCl₃): δ=14.34 (s, 1H, C⁷H), 12.66 (d, J(PH)=20.03Hz, 1H, C¹H), 8.67 (t, J(PH)=2.35 Hz, 1H, C³H), 6.98-7.90 (m, 45H, Ph),2.56 (m, 2H, C¹⁰H), 1.64 (tt, apparent quint, J(HH)=7.44 Hz, 2H, C⁹H),1.15 (t, J(HH)=7.44 Hz, 2H, C⁸H); ³¹P{¹H} NMR (242.9 MHz, CDCl₃):δ=10.91 (t, J(PP)=5.97 Hz, CPPh₃), −5.77 (d, J(PP)=5.97 Hz, IrPPh₃);¹³C{¹H} NMR (150.9 MHz, CDCl₃, plus ¹³C-dept 135, ¹H-¹³C HSQC and ¹H-¹³CHMBC): δ=230.16 (br, C⁷), 215.13 (br, C¹), 186.44 (s, C⁵), 184.96 (s,C⁶), 169.34 (dt, J(PC)=22.59 Hz, J(PC)=2.90 Hz, C⁴), 151.98 (d,J(PC)=24.44 Hz, C³), 137.51 (dt, J(PC)=62.94 Hz, J(PC)=3.21 Hz, C²),119.36-135.16 (Ph), 31.75 (s, C⁸), 31.00 (s, C¹⁰), 28.75 (s, C⁹); HRMS(ESI): m/z calculated value [C₆₄H₅₄ClP₃Ir]⁺, 143.2748; measured value,1143.2739.

Embodiment 24

The present embodiment is to describe an application of the chainmultiyne compound disclosed in the present invention in synthesizing thefused-ring metallacyclic compound (osmapentalene Os-4).

A preparation method of Os-4 is the same as that of Os-1 of embodiment18, except the following characteristics:

the HC≡CCH(OH)C≡C(CH₂)₃C≡CH used in embodiment 18 is replaced byHC≡CCH(OH)C≡CCH₂OCH₂CH═C═CH (the preparation method of this compoundrefers to embodiment 7) with an equal molar amount.

Red solid Os-4 is obtained. Yield of Os-4 is 80%. The yield of Os-4 iscalculated as a molar amount of the Os-4 divided by a molar amount ofOsCl₂(PPh₃)₃×100%.

NMR data and high resolution mass spectrometry data of the Os-4 are asfollows.

¹H-NMR (500.2 MHz, CD₂Cl₂): δ=14.01 (d, J(P,H)=17.17 Hz, 1H, C¹H), 8.21(s, 1H, C³H), 6.90-7.81 (m, 45H, Ph), 4.12 (s, 2H, C⁹H), 3.21 (s, 2H,C¹⁰H), 3.03 (s, 2H, C⁸H); ³¹P{¹H} NMR (202.5 MHz, CD₂Cl₂): δ=11.81 (d,J(P,P)=4.95 Hz, CPPh₃), −13.19 (d, J(PP)=4.95 Hz, OsPPh₃); ¹³C{¹H} NMR(125.8 MHz, CD₂Cl₂, plus ¹³C-dept 135, ¹H-¹³C HSQC and ¹H-¹³C HMBC):δ=339.19 (br, C¹), 226.16 (t, J(P,C)=4.37 Hz, C⁷), 183.46 (s, C⁵),176.00 (d, J(PC)=25.20 Hz, C⁴), 163.13 (s, C⁶), 145.12 (d, J(P,C)=21.87Hz, C³), 134.66 (dt, J(P,C)=70.73 Hz, J(P,C)=3.92 Hz, C²), 118.46-134.17(Ph), 69.92 (s, C¹⁰), 65.41 (s, C⁹), 23.08 (s, C⁸); HRMS (ESI): m/zcalculated value [C₆₄H₅₃ClOP₃Os]⁺, 1157.2607; measured value, 1157.2594.

Embodiment 25

The present embodiment is to describe an application of the chainmultiyne compound disclosed in the present invention in synthesizing thefused-ring metallacyclic compound (osmapentalene Os-5).

A preparation method of Os-5 is the same as that of Os-1 of embodiment18, except the following characteristics:

the HC≡CCH(OH)C≡C(CH₂)₃C≡CH used in embodiment 18 is replaced byPhC≡CCMe(OH)C≡CCH₂OCH₂C≡CH (the preparation method of this compound isthe same as compound 5) with an equal molar amount.

Red solid Os-5 is obtained. Yield of Os-5 is 43%. The yield of Os-5 iscalculated as a molar amount of the Os-5 divided by a molar amount ofOsCl₂(PPh₃)₃×100%.

NMR data and high resolution mass spectrometry data of the Os-5 are asfollows.

¹H-NMR (300.1 MHz, CD₂Cl₂): δ=7.05-7.72 (m, 50H, Ph), 4.45 (s, C¹H),3.78 (s, C⁸H), 2.25 (s, CH₃); ³¹P{¹H} NMR (121.5 MHz, CD₂Cl₂): δ=14.01(t, J(PP)=4.72 Hz, CPPh₃), 6.86 (d, J(PP)=4.72 Hz, OsPPh₃); ¹³C{¹H} NMR(75.5 MHz, CD₂Cl₂, plus ¹³C-dept 135, ¹H-¹³C HSQC and ¹H-¹³C HMBC): δ330.11 (br, C⁷), 225.2 (br, C¹), 171.79 (s, C⁵), 171.34 (t, J(PC)=4.94Hz, C⁶), 168.11 (dt, J(PC)=23.45 Hz, J(PC)=2.85 Hz, C⁴), 148.33 (d,J(PC)=15.37 Hz, C³), 120.25-135.76 (Ph), 118.11 (d, J(PC)=90.21 Hz, C²),71.35 (s, C⁸), 69.05 (s, C⁹), 25.12 (s, CH₃); HRMS (ESI): m/z calculatedvalue [C₇₀H₅₇ClOP₃Os]⁺, 1233.2920; measured value, 1233.2917.

The preferred embodiments of the present invention are described indetail above. However, the present invention is not limited to thespecific details of the above embodiments. Various simple modificationsmade to the technical solutions of the present invention within thescope of the technical concept of the present invention all belong tothe protection scope of the present invention.

Additionally, any combination of various embodiments of the presentinvention may also be performed as long as it does not violate thespirit of the present invention, and should also be regarded as adisclosure of the present invention.

What is claimed is:
 1. A chain multiyne compound, characterized in thatthe chain multiyne compound has a structure of Formula I shown below:

wherein X is any one of —O—, —S—, —CR₄R₅—, —SiR₆R₇— and —NR₈—; the R₄,R₅, R₆, R₇ and R₈ are any one of hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀ estergroup, C₁-C₂₀ acyl, C₃-C₂₀ cycloalkyl, C₁-C₂₀ alkyl halide, nitrilegroup, nitryl, substituted or unsubstituted aryl and

respectively and independently; the R₉ is any one of C₁-C₈ alkyl andsubstituted or unsubstituted phenyl; wherein R₁ is any one of nitrilegroup, substituted or unsubstituted C₂-C₃₀ alkynyl, substituted orunsubstituted C₄-C₃₀ multiyne, substituted or unsubstituted C₃-C₃₀cumulene group, without containing a structure unit of —C≡CCH(OH)C≡C—;R₂ and R₃ are any one of hydrogen, substituted or unsubstituted aryl,substituted or unsubstituted C₁-C₈ alkyl, substituted or unsubstitutedC₁-C₈ alkoxy, substituted or unsubstituted C₁-C₈ alkylthiol, substitutedor unsubstituted C₃-C₈ cycloalkyl and substituted or unsubstituted C₂-C₈alkynyl respectively and independently, without containing a structureunit of —C≡CCH(OH)C≡C—; wherein m and n are respectively integers from1-6, and m+n<8.
 2. The chain multiyne compound according to claim 1,characterized in that in Formula I, X is any one of —O—, —S—, —CH₂—,—C(CH₃)₂—, —CHCH₃—, —C(COOMe)₂-, —C(COOEt)₂-, —C(COCH₃)(COOMe)-,—C(Cy)(COOMe)-, —C(CH₂CH₂Br)₂—, —C(CN)₂—, —C(NO₂)₂—, —SiH₂—, —SiMe₂-,—SiPh₂-, —NH—,

R₁ is any one of nitrile group, acetenyl,

R₂ and R₃ are any one of hydrogen, methyl, ethyl, n-propyl, isopropyl,methoxyl, ethoxyl, n-propoxyl, isopropoxyl, methylthio group, ethylthiogroup, cyclopropyl, cyclohexyl,

benzyl and phenethyl, respectively and independently.
 3. The chainmultiyne compound according to claim 1, characterized in that themultiyne compound is any one of the following compounds:


4. A preparation method of the chain multiyne compound of claim 1,characterized in that, when the R₃ of the chain multiyne compound ofFormula I is hydrogen, a preparation method 1 is adopted, comprising:step a: performing a metal exchange reaction of a compound of Formula IIwith an organometallic reagent RM₁ and/or RM₂Z in an aprotic solvent,and obtaining a reaction mixture; step b: contacting and reacting theobtained reaction mixture with a compound of Formula III, obtaining areaction mixture containing a chain multiyne compound with a protectiongroup Y of Formula IV; step c: taking off the protection group Y fromthe chain multiyne compound with a protection group Y of Formula IV ofthe obtained reaction mixture in step b, and obtaining the chainmultiyne compound of Formula I:

wherein, Y is any one of trimethylsilyl (TMS), triethylsilyl (TES) andtriisopropylsilyl (TIPS); R of the organometallic reagent RM₁ and/orRM₂Z is any one of C₁-C₈ alkyl, phenyl and —NR₁₀R₁₁; wherein the R₁₀ andR₁₁ are any one of hydrogen, C₁-C₈ alkyl and trimethylsilyl,respectively and independently; M₁ is lithium, sodium or potassium; M₂is magnesium; Z is chlorine, or bromine or iodine; when the R₃ of thechain multiyne compound of Formula I is any one of: substituted orunsubstituted aryl, substituted or unsubstituted C₁-C₈ alkyl,substituted or unsubstituted C₁-C₈ alkoxy, substituted or unsubstitutedC₁-C₈ alkylthiol, substituted or unsubstituted C₃-C₈ cycloalkyl andsubstituted or unsubstituted C₂-C₈ alkynyl, a preparation method 2 isadopted, comprising: step a: performing a metal exchange reaction of acompound of Formula II with an organometallic reagent RM₁ and/or RM₂Z inan aprotic solvent, and obtaining a reaction mixture; step b: reactingthe obtained reaction mixture with a compound of Formula V, obtaining amixture containing the chain multiyne compound of Formula I:

wherein R of the organometallic reagent RM₁ and/or RM₂Z is any one ofC₁-C₈ alkyl, phenyl and —NR₁₀R₁₁; the R₁₀ and R₁₁ are any one ofhydrogen, C₁-C₈ alkyl and trimethylsilyl, respectively andindependently; M₁ of the organometallic reagent RM₁ is lithium, orsodium or potassium; M₂ of the RM₂Z is magnesium; Z of the RM₂Z ischlorine, or bromine or iodine;
 5. The preparation method of the chainmultiyne compound according to claim 4, characterized in that thepreparation method 1 also comprises using a deprotection agent to takeoff the protection group Y from the obtained chain multiyne compoundwith a protection group Y of Formula IV; wherein the deprotection agentis at least any one of K₂CO₃, Na₂CO₃, Cs₂CO₃, KF, (n-Bu)₄NF(tetrabutylammonium fluoride), (Et)₄NF (tetraethylammonium fluoride),(Me)₄NF (tetramethylammonium fluoride) and (n-Pr)₄NF(tetrapropylammonium fluoride).
 6. The preparation method of the chainmultiyne compound according to claim 5, characterized in that before thedeprotection agent takes off the protection group Y from the obtainedchain multiyne compound with a protection group Y of Formula IV,quenching and purifying processes are performed on the reaction mixtureof step a.
 7. The preparation method of the chain multiyne compoundaccording to claim 5, characterized in that after the deprotection agenttakes off the protection group Y from the obtained chain multiynecompound with a protection group Y of Formula IV, quenching andpurifying processes are performed on the obtained reaction mixture ofstep b containing the chain multiyne compound of Formula I.
 8. Thepreparation method of the chain multiyne compound according to claim 4,characterized in that the organometallic agent RM₁ of the preparationmethod 1 and 2 is at least any one of methyllithium, ethyllithium,n-butyllithium, tert-butyllithium, phenyllithium, lithiumdiisopropylamide, lithium bis(trimethylsilyl)amide; the RM₂Z is at leastany one of methylmagnesium bromide, ethylmagnesium bromide,methylmagnesium chloride and ethylmagnesium chloride.
 9. The preparationmethod of the chain multiyne compound according to claim 4,characterized in that in the preparation method 1, a molar ratio of thecompound of the Formula II to a sum of the organometallic agent RM₁and/or RM₂Z is 1:(0.5-1), preferably 1:(0.9-1); the aprotic solvent isat least any one of benzene, methylbenzene, n-haxane, ethylether,1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, petroleum ether andgasoline; the metal exchange reaction is performed of the compound ofthe Formula II and the organometallic agent RM₁ and/or RM₂Z underprotection of an inert gas; preferably, the inert gas is at least one ofnitrogen gas, helium gas, argon gas and neon gas; a condition ofcontacting the compound of the Formula II with the organometallic agentRM₁ and/or RM₂Z in an aprotic solvent, comprises a temperature at−100-30° C., preferably at −78-0° C., with time of contact for 0.5-10hours, preferably for 1-3 hours; a condition of contacting the obtainedreaction mixture by contacting the compound of the Formula II with theorganometallic agent RM₁ and/or RM₂Z in an aprotic solvent with thecompound of the Formula III, comprises a temperature at −100-30° C.,preferably at −78-0° C., with time of contact for 0.5-10 hours,preferably for 1-5 hours.
 10. The preparation method of the chainmultiyne compound according to claim 4, characterized in that in thepreparation method 2, a molar ratio of the compound of the Formula II toa sum of the organometallic agent RM₁ and/or RM₂Z is 1:(0.5-1),preferably 1:(0.9-1); the aprotic solvent is at least any one ofbenzene, methylbenzene, n-haxane, ethylether, 1,2-dimethoxyethane,tetrahydrofuran, 1,4-dioxane, petroleum ether and gasoline; the metalexchange reaction is performed of the compound of the Formula II and theorganometallic agent RM₁ and/or RM₂Z under protection of an inert gas;preferably, the inert gas is at least one of nitrogen gas, helium gas,argon gas and neon gas; a condition of contacting the compound of theFormula II with the organometallic agent RM₁ and/or RM₂Z in an aproticsolvent, comprises a temperature at −100-30° C., preferably at −78-0°C., with time of contact for 0.5-10 hours, preferably for 1-3 hours; acondition of contacting the obtained reaction mixture by contacting thecompound of the Formula II with the organometallic agent RM₁ and/or RM₂Zin an aprotic solvent with the compound of the Formula V, comprises atemperature at −100-30° C., preferably at −78-0° C., with time ofcontact for 0.5-10 hours, preferably for 1-5 hours.
 11. An applicationof a chain multiyne compound in synthesizing a fused-ring metallacycliccompound, characterized in that the chain multiyne compound is the chainmultiyne compound of Formula I according to claim
 1. 12. The applicationof a chain multiyne compound in synthesizing a fused-ring metallacycliccompound according to claim 11, characterized in that the application insynthesizing a fused-ring metallacyclic compound comprises reacting thechain multiyne compound with a metal complex; wherein the metal complexis DE_(a)L_(b); the D is any one of Fe, Co, Ni, Ru, Mn, Re, Cr, Mo, W,V, Nb, Ta, Ti, Zr, Hf, Rh, Pd, Ir, Pt and Os; the E is any one of H,halogen, SCN and CN; the L is any one of a phosphine ligand, a COligand, a pyridine ligand, a N-heterocyclic carbene ligand, a nitrileligand and an isocyanoid ligand; the a and b are integers from 0-6,respectively.
 13. The application of a chain multiyne compound insynthesizing a fused-ring metallacyclic compound according to claim 11,characterized in that the chain multiyne compound reacts with the metalcomplex; wherein the metal complex is DE_(a)L_(b); the L is any one oftrimethylphosphine, triethylphosphine, tripropylphosphine,tri-isopropylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine,triphenylphosphine, methylpyridine, ethylpyridine, 1, 4-bipyridine,1,2-bis(4-pyridyl) ethylene, vinylpyridine, pyridineboronic acid,aminopyridine, cyanopyridine, pyridinethiol, ethynylpyridine,dimethylaminopyridine, ethylene pyridine, phenylpyridine,1,2-bis(4-pyridyl)ethane, imidazole N-heterocyclic carbene, imidazolineN-heterocyclic carbene, thiazole N-heterocyclic carbene, triazoleN-heterocyclic carbene, acetonitrile, propionitrile, benzonitrile,cyclohexylisocyanide, tert-butylisocyanide and phenylisocyanide; the aand b are integers from 0-6, respectively; when a≧2, E is different oris the same and when b≧2, L is different or is the same.
 14. Theapplication of a chain multiyne compound in synthesizing a fused-ringmetallacyclic compound according to claim 11, characterized in that theapplication in synthesizing the metallacyclic compound comprisesreacting the chain multiyne compound with the metal complex; wherein themetal complex is any one of OsCl₂(PPh₃)₃, RuCl₂(PPh₃)₃, RhCl(PPh₃)₃ andIrHCl₂(PPh₃)₃.